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  • 1
    Publication Date: 1983-11-01
    Print ISSN: 0276-7333
    Electronic ISSN: 1520-6041
    Topics: Chemistry and Pharmacology
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Organometallics 2 (1983), S. 1573-1577 
    ISSN: 1520-6041
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2495-2503 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 1401). Boron, Aluminium, and Gallium Halide Adducts of a Tetraaminodiboron CompoundThe tetraamino diboron compound 1 adds trihalides EX3 (E = B, Al, Ga, X = Cl, Br, I) to yield 1:1- and 1:2-coordination compounds. The BBr3 adduct 1b is thermally stable and shows nonfluxional behaviour in solution in contrast to the AlCl3 and GaCl3 adducts. The 1:2 adducts are nonfluxional and, according to NMR spectra, only the meso-form is present. The structure of the 1:1-adducts was ascertained by an X-ray structure determination of 1g. The single crystal contained R configurated molecules. A change from planar to the envelope conformation of the diazaborolidine ring occurs on adduct formation.
    Notes: Die Tetraaminodibor-Verbindung 1 lagert die Trihalogenide EX3 (E = B, Al, Ga; X = Cl, Br, I) zu 1:1- bzw. 1:2-Koordinationsverbindungen an. Von diesen zeigt nur das thermisch stabilere BBr3-Addukt 1b in Lösung im Gegensatz zu den AlCl3- und GaCl3-Addukten kein fluktuierendes Verhalten. Die 1:2-Addukte sind starr, und nach NMR-Spektren bildet sich nur die meso-Form. Die Struktur der 1:1-Addukte wurde durch Röntgenstrukturanalyse von 1g gesichert; die Einkristalle enthielten ein R-konfiguriertes Molekül. Durch die Addition nimmt der sonst planare Diazaborolidin-Ring Briefumschlag-Konformation an.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2479-2494 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 139. Addition Compounds of Alkylhalogenoboranes with 1,3,2-Diazaborolidines: Structure, Stability, and Exchange ReactionsReactions of alkylhalogenoboranes RnBX3 - n (n = 0 - 2) with the 1,3-dimethyl-1,3,2-diazaborolidines 1 - 4 yield stable 1:1 addition compounds 1a - e, 2a, 3a - d, 4a irrespective of the boron substituents. Coordination of the borane moiety occurs at a ring N atom. An X-ray structure determination of the BCl3-adduct 3a shows two enantiomers in the asymmetric unit, envelope ring conformation, and strong π-bonding between the non-coordinated B an N atoms. - Equilibria of the 1:1 adducts with their ring cleavage products and their behaviour towards a second mol of BX3 was studied. In this case, replacement of the ring-BR group occurs. In contrast, haloboranes react with the 2-(dimethylamino)diazaborolidine 5 with R2N-substituent exchange while diborane yields in the first instance the (dimethylamino)borane adduct 5a.
    Notes: Umsetzungen von Alkylhalogenboranen RnBX3 - n (n = 0 - 2) mit den 1,3-Dimethyl-1,3,2-diazaborolidinen 1 - 4 führen unabhängig vom Bor-Substituenten zu stabilen 1:1-Additionsverbindungen 1a - e, 2a, 3a - d, 4a, wobei die Koordination über ein N-Atom des Fünfrings erfolgt. Die Röntgenstrukturanalyse des BCl3-Addukts 3a zeigt zwei enantiomere Formen in der asymmetrischen Einheit, “envelope”-Ringkonformation und eine starke π-Rückbindung des Ringbors zum nicht koordinierten Stickstoff. - Gleichgewichte der 1:1-Additionsverbindungen mit ihrem Ringöffnugsprodukt sowie ihr Verhalten gegenüber einem zweiten mol Lewis-Säure wurden untersucht. Hierbei wird die Ring-BR-Gruppe verdrängt. Im Gegensatz dazu tauscht das 2-(Dimethylamino)diazaborolidin 5 mit Halogenboranen den R2N-Substituenten aus, während die Umsetzung mit Diboran zunächst ein wenig stabiles (Dimethylamino)boran-Addukt 5a liefert.
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  • 5
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 146 Reactions of Tetrazadiborinanes with Heterocumulenes: Pseudodipolar [2 + 3]-CycloadditionsCO2, COS, and CS2 scavenge the 1,3-dipolar unit \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R'}\mathop {{\rm B - }}\limits^ \oplus {\rm NR - }\mathop {\rm N}\limits^{\rm \Theta } {\rm R} $\end{document} from the tetrazadiborinanes 3. [2 + 3]-Cycloadducts are formed in a pseudodipolar reaction, namely oxadiaza- and thiadiazaborolidines of type 7, 8 and 4. A reaction mechanism is suggested.  -  The thiadiazaborolidine 4b contains a planar five-membered ring according to an X-ray structure determination. Short BN, NN, and CN bond distances suggest a heteroaromatic ring system. High polarity is associated with the thioxo group. In contrast, the oxadiazaborolidinones 8a, b are in an equilibrium with their dimers in solution.
    Notes: CO2, COS und CS2 fangen aus den Tetrazadiborinanen 3e) den 1,3-Dipol \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R'}\mathop {{\rm B - }}\limits^ \oplus {\rm NR - }\mathop {\rm N}\limits^{\rm \Theta } {\rm R} $\end{document} ab. In einer pseudodipolaren Reaktion bilden sich als [2 + 3]-Cycloaddukte die Oxadiaza- und Thiadiazaborolidine 7, 8 und 4. Ein Reaktionsmechanismus wird diskutiert.  -  Nach Röntgenstrukturanalyse enthält 4b einen planaren Fünfring. Kurze BN-, NN- und CN-Abstände legen ein heteroaromatisches System nahe, wobei der Thioxo-Gruppe eine erhebliche Polarität zuzuweisen ist. Die Oxadiazaborolidinone 8a, b stehen in Lösung im Gleichgewicht mit ihrem Dimeren.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 398-399 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Contributions to the Chemistry of Boron, 1141) A Convenient Synthesis of Diboron TetrabromideTetramethoxydiborane (4) and boron tribromide react at ambient temperature with formation of diboron tetrabromide (yield 50%), methyl bromide and diboron trioxide. This makes B2 Br4 readily accessible for further studies.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 1884-1893 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: NMR Spectroscopic Studies of Boron Compounds, XX1) 11B- and 13C-NMR Studies of Benzanellated Heteroborolenes13C Chemical shifts of benzanellated heteroborolenes demonstrate that the BX(pp)π-interaction weakens the mesomeric donor ability of X( = O, N, S) towards the C6 ring. In addition, the comparison with isoelectronic benzanellated carbocations shows that the effect of the CX(pp)π-interaction exceeds that of the corresponding BX(pp)π-interaction.
    Notes: 13C-Chemische Verschiebungen benzanellierter Heteroborolene belegen, daß die BX(PP)π-Wechselwirkung die mesomere Donorwirkung von X ( = O, N, S) auf den C6-Ring schwächt. Der Vergleich mit isoelektronischen benzanellierten Carbokationen zeigt, daß der Effekt der CX(pp)π-den der BX(pp)π-Wechselwirkung übertrifft.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 3044-3055 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 120. Tetraorganyldiboranes(4): Preparation and Stabilitytert-Butylation of B2(OCH3)4 by LiC(CH3)3 proceeds via [(CH3)3C](CH3O)B—B(OCH3)[C(CH3)3] (1) to give tri-tert-butylmethoxydiborane(4) (2). Tetraalkylation of B2(OCH3)4 is achieved by isopropyllithium; no reaction intermediates were found in this case. Al(C2H5)3 reacts with B2(OCH3)4 to give B2(C2H5)4 which is stable only below - 30°C. On the other hand the CH3O group in 2 is replacable by CH3, and the CH3O groups in 1 by ethyl groups. Thus, product control by steric factors is evident. - The thermal stability of tetraorganyldiboranes(4) is controlled by the steric screening of the boron atoms: tetraisopropyldiborane(4) decomposes slowly at room temperature, tetraethyldiborane(4) rapidly at - 20°C.
    Notes: Die tert-Butylierung von B2(OCH3)4 mit LiC(CH3)3 führt über die Stufe [(CH3)3C](CH3O)B—B-(OCH3)[C(CH3)3] (1) zu Tri-tert-butylmethoxydiboran(4) (2). Die Tetraalkylierung von B2(OCH3)4 gelingt mit Isopropyllithium; Isopropylmethoxydiboran(4)-Zwischenstufen sind nicht faßbar. Al(C2H5)3 reagiert mit B2(OCH3)4 zu dem nur unterhalb von - 30°C stabilen B2(C2H5)4. Die CH3O-Gruppe in 2 ist gegen eine CH3-Gruppe ersetzbar, die CH3O-Gruppen von 1 gegen Ethylgruppen. Produktkontrolle erfolgt somit durch sterische Effekte. - Die thermische Stabilität der Tetraorganyldiborane(4) wird von der sterischen Abschirmung der Boratome gesteuert: Tetraisopropyldiboran(4) zersetzt sich langsam bei Raumtemperatur, Tetraethyldiboran(4) rasch bei - 20°C.
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  • 9
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: NMR Studies of Boron Compounds, XVII. 17O NMR Studies on Organyloxyboranes, Organyloxydiboranes(4), Dioxaborolanes, and Boroxins17O chemical shifts of 30 boron-oxygen compounds containing tricoordinate boron atoms can be interpreted in terms of B - O(pp)π interaction. In consonance with other physical data a decrease in the π bond order is indicated by the δ17O data along the series (R2B)2O 〉 (RBO)3 〉 R2BOR 〉 RB(OR)2 〉 B(OR)3 (R either CH3 or C2H5). Natural abundance 17O NMR spectra are recorded by PFT NMR spectroscopy in relatively short time as “routine” measurements.
    Notes: Die 17O-chemischen Verschiebungen von 30 Bor-Sauerstoff-Verbindungen, die dreifach koordiniertes Bor enthalten, sind mit B - O(pp)π-Wechselwirkung zu interpretieren. In Übereinstimmung mit anderen physikalischen Daten legen die δ17O-Werte eine Abnahme der π-Bindungsordnung in der Reihe (R2B)2O 〉 (RBO)3 〉 R2BOR 〉 RB(OR)2 〉 B(OR)3 (R = CH3 oder C2H5) nahe. 17O-NMR-Spektren von Verbindungen mit natürlicher Isotopenhäufigkeit werden mittels PFT-NMR-Spektroskopie relativ rasch in „Routinemessungen“ erhalten.
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  • 10
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, CIV. New Ring Systems Containing Diboron Units: Dithiadisilaboracyclopentanes, Dithiatriborolanes, and DithiatetraborinanesThe pyridine-catalysed comproportionation between the cyclothiasilanes 1 or 4 and the dithiatetrasilacyclohexane 2 yields the dithiatrisilacyclopentane 3. 3 reacts with R2N(Cl)B - B(Cl)NR2 (5), and the R2Si - SiR2 group is specifically eliminated from 3 yielding the dithiasiladiboracyclopentane 6, which is also obtained from 5 and 1 or 4, respectively. Further action of 5 on 6 results in the dimethylamino derivative of a dithiatetraborinane (7). Moreover, a dithiadisilaboracyclopentane (8) results from the S2Si4 system 2 and phenylborane dichloride, and finally, a dithiatriborolane (10) is obtained from 6 and CH3B(SCH3)2. The new heterocyclic compounds were fully characterized chemically and spectroscopically. The X-ray structure analysis of 6 and 7 reveals nonplanar rings with short B — N bonds.
    Notes: Die mit Pyridin katalysierte Komproportionierung der Cyclothiasilane 1 und 4 mit dem Dithiatetrasilacyclohexan 2 liefert das Dithiatrisilacyclopentan 3. Dieses reagiert spezifisch mit R2N(Cl)B - B(Cl)NR2 (5) zu einem Dithiasiladiboracyclopentan (6), ebenfalls erhältlich aus 5 und 1 bzw. 4. Mit weiterem 5 setzt sich 6 zum Dimethylamino-Derivat eines Dithiatetraborinans (7) um. Ein Dithiadisilaboracyclopentan (8) entsteht aus dem S2Si4-System 2 und Phenylbordichlorid, ein Dithiatriborolan-Derivat (10) aus 6 und CH3B(SCH3)2. Die neuen Heterocyclen werden chemisch und spektroskopisch charakterisiert. Die Röntgenstrukturanalyse sicherte für 6 und 7 nichtplanare Ringsysteme mit kurzen B — N-Bindungen.
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